Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/06—Propene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/10—Polymers of propylene
  • B29K2023/12—PP, i.e. polypropylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene

Definitions

• the present invention relates to a highly rigid propylenic resin and a blow molded article made therefrom. More particularly, it pertains to a highly rigid propylenic resin which has favorable resistance to drawdown and can produce a large sized and lightweight blow molded part being excellent in rigidity, dimensional stability and heat resistance and to a blow molded article obtained therefrom which is particularly favorably usable for bumpers such as bumpers and bumper beams for automobiles.
• Polypropylene as a resin for general purpose has heretofore been molded into a product with a desirable form and shape by any of various molding methods including extrusion molding, injection molding and blow molding.
• blow molding method has found its extensive use in molding large-sized structural materials typified by car parts because of its advantages in that molds therefor are inexpensive and that the production process can be simplified by integral molding methods.
• propylenic resin is frequently and extensively employed as raw materials from the viewpoint of specific gravity, rigidity, dimensional stability, heat resistance and the like.
• the propylenic resin for general purpose is not necessarily sufficient in satisfying rigidity or resistance to drawdown which is required in blow molding and thus, various attemps have been made to improve such properties.
• Japanese Patent Publication No. 36609/1988 corresponding to U.S. Pat. No. 4,550,145
• a process for producing propylenic resin improved in drawdown property by constituting a combination of propylene homopolymer and propylene/ethylene copolymer at a specific intrinsic viscosity and a specific compositional ratio.
• propylenic resin is not sufficient in rigidity when made into a molding, and thus further improvement has been desired.
• the present invention provides a highly rigid propylenic resin, especially a highly rigid propylenic resin which is obtained through the formation of a propylene polymer and a propylene/ethylene copolymer by multistage polymerization, said resin having a melt index MI! in the range of 0.1 to 1.2 g/10 minutes as determined at a temperature of 230° C. under a load of 2,160 g and also satisfying a relationship between the MI! and the elongational viscosity Y(Pa ⁇ s)!, said relationship being represented by the expression
• the melt index MI! determined at a temperature of 230° C. under a load of 2,160 g in accordance with JIS K-7210 be in the range of 0.1 to 1.2 g/10 minutes.
• An MI value less than 0.1 g/10 minutes brings about a remarkable decrease in the throughput quantity, thus deteriorating the productivity of the resin, whereas that more than 1.2 g/10 minutes makes it impossible to form a large-sized blow molded article.
• the MI is preferably in the range of 0.2 to 1.0 g/10 minutes.
• the propylenic resin according to the present invention satisfies a relationship between the MI and the elongational viscosity Y(Pa ⁇ s)!, said relationship being represented by the expression
• a Y value less than 2.0 ⁇ 10 5 ⁇ MI -0 .68 results in severe drawdown of a parison at the time of blow molding, making it difficult to form a large-sized blow molded article weighing 5 kg or more, whereas that more than 8.0 ⁇ 10 5 ⁇ MI -0 .68 leads to deterioration of the extrusion characteristics as well as the external appearance of the blow molded article.
• the elongational viscosity Y(Pa ⁇ s)! is measured with a stretch rheometer (for example, produced by Iwamoto Manufacturing Co., Ltd.) by the use of a bar sample with c.a. 3 mm diameter and 20 cm length by allowing the sample to stand in a silicone oil at 175° C. for 15 minutes under the conditions including 175° C. temperature, 0.05 sec -1 strain velocity and 2.0 strain.
• a stretch rheometer for example, produced by Iwamoto Manufacturing Co., Ltd.
• the process for producing the propylenic resin according to the present invention is not specifically limited provided that the process is capable of producing a propylenic resin which satisfies the above-mentioned conditions.
• Examples of the aforesaid stereoregular catalyst to be used for the multistage polymerization include a catalyst comprising a halogenide of a transition metal, an organoaluminum compound and a substance to be added for preparing a polymer having improved stereoregularity and a broad molecular weight distribution such as a lactone.
• Examples of the halogenide of a transition metal preferably include halogenides of titanium, of which titanium trichloride is particularly preferable.
• the titanium trichloride is exemplified by that prepared by reducing titanium tetrachloride through any of various methods; that prepared by further activating the preceding titanium tetrachloride through any of various methods; that prepared by further activating the preceding titanium trichloride by means of a treatment in a ball mill and/or solvent cleaning (for example, cleaning with an inert solvent or an inert solvent containing a polar compound); and that prepared by subjecting titanium trichloride or a titanium trichloride eutectic such as TiCl 3 .1/3 AlCl 3 to a crushing treatment together with an amine, an ether, an ester, sulfur, a halogen derivative or an organic or inorganic nitrogen or phosphorus compound.
• a halogenide of titanium supported on a magnesium-based carrier there is also usable
• organoaluminum compound examples include a compound represented by the general formula (I)
• R is an alkyl group having 1 to 10 carbon atoms
• X is a halogen atom
• n is a number satisfying 0 ⁇ n ⁇ 3.
• organoaluminum compound examples include dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride and triethylaluminum.
• the organoaluminum compound may be used alone or in combination with at least one other. It is used in an amount of usually 1 to 100 moles per one mole of the above-mentioned halogenide of a transition metal.
• Example of lactones include a compound represented by the general formula (II) ##STR1## wherein R 1 and R 2 are each a hydrogen atom or a hydrocarbon group having at most 20 carbon atoms and belonging to saturated aliphatic series, unsaturated aliphatic series, alicylic series or aromatic series, and may be the same as or different from each other, and m is an integer from 2 to 8.
• lactone of the general formula (II) mention is made of ⁇ -lactons such as ⁇ -butyroloctone, ⁇ -valerolactone, ⁇ -caproloctone, ⁇ -capryloctone, ⁇ -laurolactone, ⁇ -palmilactone, ⁇ -stearolacton; ⁇ -lactones such as ⁇ -valerolactone and ⁇ -caproloctone; ⁇ -lactons such as ⁇ -caprolactone; and ⁇ -loctones such as ⁇ -propiolactone and dimethylpropiolactone.
• ⁇ -lactons such as ⁇ -butyroloctone, ⁇ -valerolactone, ⁇ -caproloctone, ⁇ -capryloctone, ⁇ -laurolactone, ⁇ -palmilactone, ⁇ -stearolacton
• ⁇ -lactones such as ⁇ -valerolactone and ⁇ -caproloctone
• ⁇ -lactons such as ⁇ -cap
• lactones Of these lactones, ⁇ -loctones and ⁇ -lactones are preferable, and ⁇ -butyrolactone, ⁇ -caprolactone and ⁇ -caproloctone are particularly preferable. Any of these lactones may be used alone or in combination with at least one other. It is used in an amount of usually 0.01 to 10 moles per one mole of the above-mentioned halogenide of a transition metal.
• the first stage it is preferable in the first stage to carry out the polymerization of propylene at a temperature of 50° to 70° C. so as to produce a propylene polymer having an intrinsic viscosity ⁇ ! of 0.5 to 3.5 dL (deciliter)/g (in decalin, 135° C.) in an proportion of 60 to 80% by weight based on the whole amount of the polymer.
• An intrinsic viscosity ⁇ ! of the propylene polymer less than 0.5 dL/g brings about a low impact strength of the propylenic resin to be produced, whereas that more than 3.5 dL/g causes a decrease in throughput quantity of the resin at the time of blow molding, in certain cases.
• a proportion of the polymer produced in the first stage less than 60% by weight results in insufficient rigidity of the propylenic resin to be produced, whereas that more than 80% by weight gives rise to deterioration of the impact strength thereof, in certain cases.
• the second stage it is preferable in the second stage to carry out the polymerization of propylene at a temperature of 50° to 70° C. so as to produce a propylene polymer having an intrinsic viscosity ⁇ ! of 3.5 to 5.5 dL/g (in decalin, 135° C.) in a proportion of 10 to 20% by weight based on the whole amount of the polymer.
• An intrinsic viscosity ⁇ ! of the propylene polymer less than 3.5 dL/g brings about a low impact strength of the propylenic resin to be produced, whereas that more than 5.5 dL/g causes a decrease in throughput quantity of the resin at the time of blow molding, in certain cases.
• a proportion of the polymer produced in the second stage less than 10% by weight results in insufficient rigidity of the propylenic resin to be produced, whereas that more than 20% by weight gives rise to deterioration of the impact strength thereof, in certain cases.
• the third step it is preferable in the third step to carry out the copolymerization of propylene and ethylene at a temperature of 45° to 65° C. so as to produce a propylene/ethylene copolymer having an intrinsic viscosity ⁇ ! of 3.5 to 5.5 dL/g (in decalin, 135° C.) and an ethylene unit content of 40 to 75% by weight in a proportion of 8 to 15% by weight based on the total amount of the polymer.
• An intrinsic viscosity ⁇ ! of 3.5 to 5.5 dL/g (in decalin, 135° C.) and an ethylene unit content of 40 to 75% by weight in a proportion of 8 to 15% by weight based on the total amount of the polymer.
• a proportion of the copolymer produced in the third stage less than 8% by weight results in a low impact strength of the propylenic resin to be produced, whereas that more than 15% by weight gives rise to deterioration of the rigidity thereof, in certain cases.
• An ethylene unit content of less than 40% by weight in the copolymer results in a low impact strength of the propylenic resin to be produced, whereas that of more than 60% by weight leads to deterioration of the rigidity, in certain cases.
• the ethylene unit content in the copolymer can be obtained by measuring infrared absorption spectrum.
• the modulation for the intrinsic viscosity ⁇ ! of the polymer in each of the stages can be carried out, for example, by properly altering the concentration of a molecular weight modulator such as hydrogen.
• the pressure in the polymerization reaction is selected in each stage in the range of usually atmospheric pressure to 30 kg/cm 2 G, preferably 1 to 15 kg/cm 2 G.
• the polymerization system there are applicable a continuous method by using at least three polymerization vessels, a batchwise method by using at least one polymerization vessel and a method by the combination of the above-mentioned continuous method and batchwise method.
• the polymerization method there are adoptable, without specific limitation, suspension polymerization, solution polymerization, gas-phase polymerization or the like.
• solvent when used, mention is made of an aliphatic hydrocarbon such as heptane and hexane, an alicyclic hydrocarbon such as cyclohexane and an aromatic hydrocarbon such as benzene and toluene. Any of the solvents may be used alone or in combination with at least one other.
• the propylenic resin thus obtained according to the present invention has favorable resistance to drawdown and can afford a large-sized blow molded part which is lightweight and excellent in rigidity, dimensional stability and heat resistance.
• the blow molded article according to the present invention is produced through the blow molding of the above-mentioned propylenic resin by blending therewith as desired, any of additives such as soft elastomer, modified polyolefin, antioxidant, heat resistant stabilizer, weather resistance stabilizer, inorganic or organic filler, nucleating agent, antistatic agent, chlorine scavenger, slip agent, flame retardant and coloring agent.
• any of additives such as soft elastomer, modified polyolefin, antioxidant, heat resistant stabilizer, weather resistance stabilizer, inorganic or organic filler, nucleating agent, antistatic agent, chlorine scavenger, slip agent, flame retardant and coloring agent.
• the blow molding method there is usable, without specific limitation, a method which has been customarily employed in the blow molding of propylenic resin.
• the blow molded article according to the present invention is lightweight and excellent in rigidity, dimensional stability and heat resistance, and is preferably used particularly for bumpers including car bumpers and car bumper beams.
• the intrinsic viscosity ⁇ ! of the polymer in each of the stages is that measured in decalin at 135° C.
• a 10 L (liter) autoclave equipped with a stirrer was charged with 4L of n-heptane, 5.7 mmol of diethylaluminum chloride, 0.7 g of titanium trichloride and 0.2 mL (milliliter) of ⁇ -caprolactone.
• the autoclave was continuously fed with hydrogen which had been weighed so as to attain a prescribed intrinsic viscosity ⁇ ! of the propylene polymer to be produced and with propylene so as to attain a reaction pressure of 9 kg/cm 2 G, while the liquid-phase temperature was maintained at 60° C., to carry out the first stage reaction under stirring for 90 minutes.
• the unreacted propylene was removed, and hydrogen thus weighed along with propylene were continuously fed in the autoclave so as to attain a reaction pressure of 7 kg/cm 2 G, while the temperature therein was maintained at 60° C., to carry out the second stage reaction for 40 minutes.
• the intrinsic viscosity ⁇ ! and the polymerization amount of the polymer obtained in each of the polymerization stages are given in Table 1. Further, the physical properties of the objective propylenic resin are given in Table 2
• Example 2 The procedure in Example 1 was repeated to carry out the polymerization except that the intrinsic viscosity ⁇ ! and the polymerization amount of the polymer obtained in each of the polymerization stages were altered as shown in Table 1. The results obtained are given in Table 2.
• Example 2 The procedure in Example 1 was repeated to carry out the polymerization except that the intrinsic viscosity ⁇ ! and the polymerizaiton amount of the polymer otained in each of the polymerization stages were altered as shown in Table 1. The results obtained are given in Table 2.
• Example 2 To the polymer which had been obtained in Example 1 was added 0.1% by weight of sodium salt of methylenebis(2,4-di-tert-butylphenol) acid phosphate as the nucleating agent to form a propylenic resin.
• the physical properties thereof are given in Table 2.
• a 10 L(liter) autoclave equipped with a stirrer was charged with 5 L of dehydrated n-hexane, 1.0 g of diethylaluminum chloride and 0.3 g of titanium trichloride.
• the autoclave was continuously fed with hydrogen which had been weighed so as to attain a prescribed intrinsic viscosity ⁇ ! of the propylene polymer to be produced and with propylene so as to attain a reaction pressure of 9 kg/cm 2 G, while the liquid-phase temperature was maintained at 65° C., to carry out the first stage reaction under stirring for 90 minutes. Subsequently, the unreacted propylene was removed, and the liquid-phase temperature was lowered to 50° C.
• the mixture of propylene and ethylene and hydrogen thus weighed were continuously fed in the autoclave so as to attain a reaction pressure of 9 kg/cm 2 G, while the temperature therein was maintained at 50° C., to carry out the third stage reaction for 30 minutes. Then, the unreacted gas was removed, and to the resultant polymerization product was added n-butanol, and the mixture was stirred at 65° C. for one hour to decompose the catalyst and was subjected to the steps of separation, cleaning and drying with result that a polymer in the form of white powder was obtained.
• the polymerization was carried out by altering the intrinsic viscosity ⁇ ! and the polymerization amount of the polymer in each of the polymerization stages as given in Table 1. Further, the physical properties of the objective polypropylenic resin are given in Table 2.
• Example 2 The procedure in Example 1 was repeated to carry out the polymerization except that the addition of ⁇ -caprolactone as the catalyst was omitted.
• the intrinsic viscosity ⁇ ! and the polymerization amount of the polymer in each of the polymerization stages are given in Table 1, and the physical properties of the objective propylenic resin are given in Table 2.
• Example 2 The procedure in Example 1 was repeated to carry out the polymerization except that the intrinsic viscosity ⁇ ! and the polymerization amount of the polymer obtained in each of the polymerization stages were altered as shown in Table 1. The results obtained are given in Table 2.
• Example 2 The procedure in Example 1 was repeated to carry out the polymerization except that the polymerization was performed in two stages instead of three stages and instead, the polymerization amount in the first stage was increased.
• the instrinsic viscosity ⁇ ! and the polymerization amount of the polymer in each of the polymerization stages are given in Table 1, and the physical properties of the objective propylenic resin are given in Table 2.
• the mixture having the under-mentioned composition was incorporated with a prescribed antioxidant and thereafter was kneaded by the use of a bidirectional twin-screw kneader (produced by Kobe Steel Ltd., model 2FCM) at a temperature set to 200° C. at a number of screw revolutions of 800 r.p.m, while the temperature of the resulting melt was 250° C.
• the kneaded product was formed into strands by means of an extruder, and then granulated with a pelletizer to produce a composite material for bumper beam.
• Table 2 The results of the measurement of the physical properties are given in Table 2.
• Polypropylene (ethylene unit content: 5% by weight, MI: 0.9 g/10 minutes) 70% by weight
• High density polyethylene (HLMI: 3.8 g/10 minutes) 20% by weight
• HLMI indicates MI (melt index) measured under the conditions of 190° C. temperature and 21.6 kg load.
• Propylenic resin for a bumper beam parison with necessary length/weight of 1900 mm/10 kg and that for a bumper parison with necessary length/weight of 2600 mm/15 kg were each injected from an accumulator to form a parison.
• the moldability was evaluated by the variation in the length of the parison during 5 seconds, that is, the mold closing time.
• Thickness distribution was evaluated by measuring the thickness of each of the cross sections of the blow molded article.
• Product rigidity was evaluated by comparing its distorsion with that of a steel-made product.
• a fusing adhesion part which is called pinch-off part is formed at the time of mold closing by the fusing adhesion of the inside of a parison with each other.
• the pinch-off part is apt to become a starting point of rupture or break, and thus a structural part and a part requiring strength are needed to be improved in the fusing adhesivity of the pinch-off part. Accordingly, the fusing adhesivity of the pinch-off part was evaluated by the following procedure.
• Example 4 By the use of each of the resins that had been obtained in Example 4 and Comparative Examples 6, a bottle having a prescribed shape was prepared by blow molding, and a strip test piece with 20 mm width was cut out from the bottom of the bottle so as to include the pinch-off in the width direction.
• the test piece thus obtained was notched with a notching blade of 2.0 mm in R at both the ends of the pinch-off part so that the pinch-off part had 10 mm width.
• the test piece was tested at a tensile velocity of 50 mm/minute by the use of a tensile test machine (produced by INSTRON Corp. in U.S.A under the tradename INSTRON 1125). The yield strength and rupture energy were regarded as the index of the pinch-off strength.
• the enhancement of the fusing adhesivity increases with an increase in each of the foregoing values.
• the yield strength is represented by the maximum stress value in the stress strain diagram
• the rupture energy is represented by the product (stress) ⁇ (strain)! which is obtained by integrating the stress with respect to the strain from zero to the rupture point in the range of the strain.
• the rupture energy can be shown by the area which is surrounded by the stress strain diagram and the abscissa.
• a bumper beam which had been obtained by blow molding each of the resins as discoveredd in Example 4 and Comparative Example 6 was subjected to pendulum test in accordance with Federal Motor Vehicle Safety Standards (abbreviated to FMVSS) PART 581.
• FMVSS Federal Motor Vehicle Safety Standards
• the bumper beam was fitted to a bogie of 1000 kg in weight, and an impact ridge of 1000 kg in weight was allowed to collide with the bumper beam at a velocity of 5 miles/hour (about 8 km/hour) to obtain the relation between the generated load and the distortion size of the beam, while the place of the collision was made to the central part of the beam.
• the test temperatures were each set to a high temperature (50° C.), ordinary temperature (23° C.) and a low temperature (-10° C. and -30° C.) taking into consideration of the conditions under which the bumper beam is mounted on a commercial car.
• the evaluation was carried out by the maximum distortion and the occurrence of crack.
• Example 8 has been demonstrated in Table 5 that the yield strength in Example 8 is about 1.7 times that in Comparative Example 12 and the fusing adhesivity in Example 8 expressed in terms of rupture energy is about 10 times that in Comparative Example 12. It is thought that the manifestation of the excellent impact resistant in the pendulum test in Example 8 is due to the remarkable improvement in the fusing adhesivity of the pinch-off part.
• blow molded articles obtained from the highly rigid propylenic resin according to the present invention are favorably usable particularly for large-sized car parts such as bumpers, bumper beams, seat back and instrument panels.

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• Chemical & Material Sciences (AREA)
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• Mechanical Engineering (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1995
  • 1995-07-14 DE DE69526324T patent/DE69526324T2/de not_active Expired - Fee Related
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  • 1995-07-14 WO PCT/JP1995/001406 patent/WO1996002381A1/ja active IP Right Grant
• 1997
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